JPH1111985A - Glass article coated with ultraviolet ray absorbable colored film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a glass article coated with an ultraviolet ray absorbable colored film, in which color tone, ultraviolet ray transmission and visible ray transmission are controlled. SOLUTION: The article is obtained by applying an ultraviolet ray absorbable film containing 5-50 wt.% silicon oxide, 20-70 wt.% titanium oxide and 25-75 wt.% cerium oxide as main components on the surface of a glass substrate and forming a top layer containing 55-90 wt.% silicon oxide, 1.0-10 wt.% titanium oxide, 1.0-15 wt.% cerium oxide and 5-20 wt.% gold particulates for coloring and having a lower refractive index than that of the ultraviolet ray absorbable film on the ultraviolet ray absorbable film, and the visible ray transmission is >=70%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass article coated with an ultraviolet absorbing colored film, and more particularly to a glass sheet coated with an ultraviolet absorbing colored film used for vehicles such as automobiles and windows of buildings. It is.

[0002]

2. Description of the Related Art As a method for obtaining a colored glass, an inorganic salt of silver or copper is applied to a glass surface and then baked, whereby fine particles of silver or copper penetrate into a glass substrate to form a transparent colloidal color. There is a method in which gold ions are mixed with a metal alkoxide solution and applied to a substrate, followed by heat treatment to precipitate gold fine particles. Another method is to form a metal film deposited on a glass substrate by a sputtering method.

On the other hand, an ultraviolet absorbing film is formed by forming a metal oxide such as zinc oxide, titanium oxide, and cerium oxide, which are ultraviolet absorbing components, on a glass substrate by a sol-gel method or a sputtering method. Ce
JP-A-6-192598 describes that an ultraviolet absorbing film containing O ₂ : TiO ₂ : SiO ₂ at a ratio of 64:18:18 is formed on a glass substrate by a sol-gel method.

The above-mentioned films are colored but do not have an ultraviolet absorbing ability, or have an ultraviolet absorbing ability but are not colored. Also, JP-A-6-19189
No. 6 discloses a colored film containing silicon oxide, titanium oxide and gold fine particles, for example, TiO ₂ 8 as a preferable composition.
5-3 wt%, SiO ₂ 40 to 0 wt%, Au. 5 to
Glass articles coated with a colored film in the range of 60% by weight are described. However, this colored film-coated glass article has a T
When the iO ₂ content is not high, the ultraviolet ray blocking performance is not sufficient, and when the TiO ₂ content is high, a high ultraviolet ray blocking performance can be obtained. , And the visible light transmittance cannot be freely controlled.

[0005] Recently, even in the float method, a glass substrate having a drastically improved ultraviolet cut property by cerium ions or the like has been produced, and has been actively used for automotive glass and the like. However, there are still few types of glass substrates having an ultraviolet cut property, while glass plates having various functions and colors are required in the market.

[0006] An application filed by the present applicant, Japanese Patent Application No. 8-392.
In No. 26, by coating a thin film containing silicon oxide as a main component and containing fine gold particles on a glass substrate,
Glasses with various colors have been obtained. Also, in Japanese Patent Application No. 8-339412, a glass article having an ultraviolet shielding property and having various colors is obtained by coating a glass substrate with a thin film obtained by combining an ultraviolet absorbing film and a film containing gold fine particles. Have been. Among them, a glass substrate colored in green (green) is coated with a pink colored film, and a colored glass article having a transmission color of gray (gray) in a complementary color relationship is obtained. Since this glass article uses a green-colored glass substrate for the substrate, it has better heat rays than the conventional gray-colored glass plate,
Has the ability to cut ultraviolet rays.

However, the glass plate obtained by coating the above-mentioned thin film on the green colored glass substrate tends to have low visible light transmittance, and from the viewpoint of ensuring the visibility of a glass window for an automobile, in particular, a driver, visible light of 70% or more is legally required. It has not been easy to apply this to front doors and windshields that require light transmittance. The above-mentioned Japanese Patent Application No. Hei 8-
No. 339,412 describes an example in which an ultraviolet absorbing film is coated on a green substrate, and then a pink colored film is further coated thereon. Only those having a transparent color were obtained.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a glass article coated with an ultraviolet-absorbing colored film having a controlled color tone, ultraviolet transmittance and visible light transmittance.

[0009]

That is, the present invention provides an ultraviolet absorbing colored film coating characterized by adding a small amount of titanium oxide and cerium oxide to a film composition utilizing silicon oxide as a main component and utilizing the coloring of gold fine particles. It is a glass article.

That is, in the present invention, a glass substrate surface is coated with an ultraviolet absorbing film containing, as a main component, 5 to 50 silicon oxide, 20 to 70 titanium oxide, and 25 to 75 cerium oxide in weight%. The ultraviolet light, which contains, in terms of% by weight, silicon oxide 55 to 90, titanium oxide 1.0 to 10, cerium oxide 1.0 to 15, and gold fine particles for coloring 5 to 20 in terms of% by weight on the ultraviolet absorbing film. Visible light transmittance of 70% formed by forming an upper layer having a lower refractive index than that of the absorbing film
The above is a glass article coated with an ultraviolet absorbing colored film.

The above ultraviolet absorbing film (lower layer) in the present invention
Each component of the composition is described below. Silicon oxide is necessary to maintain the strength of the film. If the content is too low, the strength of the film will be low, and the visible light reflectance of the glass article coated with the ultraviolet absorbing colored film will be too high. Conversely, if the amount is too large, the ultraviolet absorption performance is reduced. Therefore, the content of silicon oxide is from 5 to 50% by weight in terms of SiO _2, preferably 10 to 30 wt%.

[0012] Titanium oxide is necessary for forming a film containing silicon oxide and cerium oxide. If the content is too low, the film-forming property and transparency of the film are deteriorated, and the ultraviolet absorbing power is reduced. Also decrease. Conversely, if it is too large, the refractive index of the film increases and the visible light reflectance becomes too high. Therefore,
The content of titanium oxide is 20 to 70% by weight in terms of TiO _2, preferably 25 to 50% by weight, more preferably 28 to 40 wt%.

Cerium oxide is a component necessary for absorbing ultraviolet rays, and if its content is too low, its ability to absorb ultraviolet rays decreases. Conversely, if the amount is too large, the transparency of the film is reduced, the film forming property is reduced, and the durability of the film is also reduced. Therefore, the content of cerium oxide is 25 to 75 in terms of CeO _2.
%, Preferably 25 to 60% by weight, more preferably 40 to 57% by weight.

If the thickness of the ultraviolet absorbing film is too small, the ultraviolet absorbing ability is lowered, and if it is too large, the film strength is reduced. Therefore, the thickness is preferably from 60 to 250 nm, more preferably 90 to 250 nm. ２００200 nm, more preferably 110-160 nm. The ultraviolet absorbing film has a refractive index (632.8 n) of 1.63 to 2.20.
Value for light of wavelength m. Hereinafter, the value of the refractive index is a value at this wavelength unless otherwise specified).

Next, the upper layer mainly composed of silicon oxide, which is formed on the ultraviolet absorbing film, will be described. The upper layer contains fine particles for coloring silicon oxide, titanium oxide, cerium oxide, and gold, and has a refractive index lower than the refractive index of the ultraviolet absorbing film. Silicon oxide is necessary as a low-refractive-index material for causing the film to develop a reddish color due to the fine gold particles. If the content is too small, the coloration of the fine gold particles shifts to a bluish color and a desired color tone cannot be obtained. . Therefore, the content of silicon oxide is 55 to 90% by weight, preferably 65 to 90% by weight, more preferably 7 to 70% by weight in terms of SiO _2.
5 to 90% by weight.

Titanium oxide and cerium oxide are:
By adjusting the refractive index of the uppermost film, it changes the plasmon absorption of the fine gold particles and acts as a color tone adjuster that adjusts the subtle color tone, as well as the function of uniformly dispersing and supporting the fine gold particles in the film. have. That is,
If an upper layer film containing only gold fine particles and silicon oxide is formed on a 100% silicon oxide base film by a sol-gel method, the gold fine particles are uniformly dispersed in the upper layer film to produce a desired color.

However, if an attempt is made to form an upper layer containing only gold fine particles and silicon oxide on the above-mentioned ultraviolet absorbing film whose base contains titanium oxide and cerium oxide by a sol-gel method, the cause has not been elucidated. As a result, it is difficult for gold particles to be uniformly deposited in the upper layer film, and the diameter of the gold particles increases, or gold is not uniformly dispersed in the film and is deposited unevenly on the underlying surface of the film. In addition, the color development by the fine gold particles tends to be insufficient.

In the present invention, by containing titanium oxide and cerium oxide in the upper layer containing gold and silicon oxide, the fine gold particles can be uniformly deposited in the upper layer, so that the color development by the desired fine gold particles can be achieved. Is obtained. However, if the contents of titanium oxide and cerium oxide are too large, the refractive index of the upper layer becomes high, and the visible light reflectance of the glass article coated with the ultraviolet absorbing colored film cannot be lowered. Therefore the titanium oxide content of 1.0 to 10% by weight in terms of TiO _2, more preferably 1.0 to 8 wt%, more preferably 1.3 to 5 wt%, cerium oxide content CeO 1.0 to 15% by weight in terms of ₂ ,
Preferably 1.5 to 10% by weight, more preferably 2.
0 to 7% by weight.

The fine gold particles are necessary for imparting a red color to the upper layer as described above, and are chemically stable.
Fine particles can be produced relatively easily. If the content is too low, sufficient coloring cannot be obtained, and if it is too high, the durability of the film decreases. Therefore, the content of the gold fine particles for coloring is 5 to 20% by weight, preferably 5 to 17% by weight, and more preferably 8 to 14% by weight.

If the refractive index of the upper layer is too high, the visible light reflectance cannot be lowered as described below.
Titanium oxide and cerium oxide are added to silicon oxide so that the refractive index is 1.40 to 1.60 and lower than the refractive index of the ultraviolet absorbing film by at least 0.10, and more preferably by at least 0.2. Adjusted. The more preferable value of the refractive index of the upper layer is 1.45 to 1.55. If the thickness of the upper layer is too small, the ability to retain the gold fine particles for coloring is reduced. Conversely, if the thickness is too large, the film tends to be cracked or the substrate glass is liable to be deformed such as warping during firing. It is preferable to set the thickness to 45 to 120 nm so that the reflection color of light projected from the glass surface side is as close as possible to neutral gray.
More preferably, the thickness is 50 nm to 90 nm. By providing an upper colored film having a refractive index lower than the refractive index of the ultraviolet absorbing film on the ultraviolet absorbing film, the reflectance of visible light can be reduced, and the light projected from the glass surface side can be reduced. The reflection tone can be adjusted so as to be a color close to neutral gray.

Assuming that the refractive index of the lower refractive index upper layer is n ₂ , the refractive index of the ultraviolet absorbing film is n ₁ , and the refractive index of air is n ₃ , the nonreflection condition for the refractive index is n ₂ = (n ₁ × n ₃ ) ^1/2
Since n ₃ = 1, the non-reflection condition is n ₂ = n ₁ ^1/2 . Even if the refractive index n ₂ of the low refractive index upper layer slightly deviates from this equation, the antireflection effect is large. Therefore, n ₂ is 90 to 117% of the square root of the refractive index of the ultraviolet absorbing film, that is,

It is preferable that the formula (1) of 1.17 × n ₁ ^1/2 ≧ n ₂ ≧ 0.90 × n ₁ ^1/2 (1) is satisfied, more preferably 95 to 114%. . The refractive index of the ultraviolet absorbing film is set to 1.80 in order to obtain a non-reflection condition with the lower refractive index upper layer.
It is preferable that it is above.

The gold fine particles for coloring show different colors depending on the value of the refractive index of the matrix. The gold fine particles are colored near blue when the refractive index of the matrix is high, and are pink when the refractive index of the matrix is low. Color to a close color. Here, when gold fine particles are contained in the lower refractive index upper layer, the film itself shows reddish coloring. Therefore, a glass article coated with an ultraviolet absorbing film and a colored film shows a composite color of the color of the substrate itself and the color of the colored film.

When the glass plate having the ultraviolet absorbing and coloring film having the above two-layer structure is mounted on an automobile window such that the coating surface of the glass plate is on the inside of the vehicle, the visible light reflectance as viewed from the inside of the vehicle is low. If the height is too high, the visibility of interior materials may be obstructed by the driver, so the reflectance of visible light when light is incident from the coated surface side of the glass plate should be as small as possible, about 20% or less. Is preferably 1
It is more preferably at most 5%, more preferably at most 10%.
In addition, if the visible light reflectance seen from the outside of the vehicle is too high, the appearance becomes glaring. Therefore, the visible light reflectance when light is incident from the side opposite to the coated surface of the glass plate is about 20%.
It is preferably as small as possible below, more preferably 15% or less, more preferably 10% or less.

The combination of the refractive index of the UV absorbing film and the refractive index of the low refractive index upper layer makes it possible to reduce the reflectance of visible light on the coated surface side and the glass surface side.
A glass plate coated with an ultraviolet absorbing colored film having a visible light transmittance of 0% or more is obtained. The reflection color tone, particularly the reflection color tone when the light is incident from the glass surface side opposite to the coating surface of the glass plate (the color tone of the glass plate viewed from the outside of the vehicle) is preferably close to neutral gray in appearance. A and b in color system
(A ² + b ² ) ^1/2 (saturation) calculated from the value of
It is preferably 0 or less, more preferably 8.0 or less, and still more preferably 5.0 or less.

Further, as the glass substrate in the present invention,
By using a 1.5 to 5.5 mm thick transparent glass substrate colored green, an ultraviolet and heat shielding glass plate having a transmission color close to neutral gray can be obtained.

As an example, the Lab color system is -7.0.
By combining a value of a of -3.0 with a green colored glass plate having a transmitted light chromaticity of b of -1.0 to 4.0, a transmission color close to neutral gray, especially a Lab color system A UV-absorbing colored coated glass plate having a transmitted color in which the value of the transmitted light chroma (a ² + b ² ) ^1/2 calculated from the values of the transmitted light chromaticities a and b is 5.0 or less is obtained. Can be The colored film itself shows a reddish color due to the fine gold particles, but this color is combined with the green color of the glass substrate in a complementary color relationship,
A colored coated glass plate with a color close to neutral gray is obtained.

Further, by using a glass plate having an ultraviolet ray blocking performance and a heat ray blocking performance as a substrate, a high performance gray glass plate having a UV cut function which is not available in the conventional gray glass can be obtained. If the refractive index of the colored film becomes too large, the film itself shows a bluish color, and even when combined with the above-mentioned green glass substrate, a color close to neutral gray cannot be obtained and the color becomes more bluish green.

As a raw material of the silicon oxide, titanium oxide and cerium oxide for forming the ultraviolet absorbing film and the upper layer film in the present invention, any material can be used as long as it can form a transparent film by a sol-gel method. .

As a raw material of silicon oxide, a metal alkoxide is preferable, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. In addition, these condensates (n ≧
2) or a mixture of condensates is also conveniently used. For example, as the condensate, hexaethoxydisiloxane (n = 2), octaethoxytrisiloxane (n = 2)
3), decaethoxytetrasiloxane (n = 4), ethoxypolysiloxane (n ≧ 5) and the like can be used. Ethyl silicate 40 consisting of a mixture of a monomer (n = 1) and a condensate (n ≧ 2) [composition: Cihlar literature,
Colloids and Surfaces A: Physicochem.Eng.Aspects
70 (1993) pp. 253 to 268, and by weight fraction monomer (n = 1): 12.8% by weight, dimer (n
= 2): 10.2% by weight, trimer (n = 3): 12.0
% By weight, tetramer (n = 4): 7.0% by weight, multimer (n
≧ 5): 56.2% by weight, ethanol: 1.8% by weight)
Is preferably used.

In addition, an alkyl trialkoxysilane in which the alkoxy group of the above compound is substituted with an alkyl group can also be used. For example, an alkoxy group is a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group,
Alkenyl such as a linear or branched alkyl group such as an octyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a vinyl group, an allyl group, a γ-methacryloxypropyl group, and a γ-acryloxypropyl group. Groups, phenyl groups, toluyl groups, aryl groups such as xylyl groups, aralkyl groups such as benzyl and phenethyl groups, or γ-mercaptopropyl groups, γ-chloropropyl groups, and γ-aminopropyl groups. .

As a raw material of titanium oxide, an organic compound of titanium such as titanium alkoxide, titanium acetylacetonate, and titanium carboxylate is preferably used. As the titanium alkoxide, generally, Ti (OR)
₄ (R is an alkyl group having up to 4 carbon atoms)
Considering the reactivity, titanium isopropoxide and titanium butoxide are preferable. It has also been known that in the case of titanium, the use of acetylacetonate is preferable in terms of its stability. In this case, as a general formula, Ti (OR) mLn (m + n = 4, n ≠ 0), where L is acetylacetone. In this case,
Titanium alkoxide may be acetylacetonated with acetylacetone, or commercially available titanium acetylacetonate may be used. It is further conceivable to use a carboxylate.

As a raw material for cerium oxide, cerium organic compounds such as cerium alkoxide, cerium acetylacetonate, and cerium carboxylate can be suitably used. In addition, nitrates, chlorides,
Cerium inorganic compounds such as sulfates can also be used, but cerium nitrate and cerium acetylacetonate are preferred from the viewpoint of stability and availability.

As a raw material of the gold fine particles for coloring used in the present invention, a chloride such as chloroauric acid is suitable, but is not particularly limited as long as it is stable and soluble.

When alkoxides are used as a silicon oxide raw material, a titanium oxide raw material, and a cerium oxide raw material, examples of the hydrolysis catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, acetic acid, oxalic acid, formic acid, propionic acid, and p-acid. Organic acids such as toluenesulfonic acid are used.

The coating liquid for coating the ultraviolet absorbing film and the upper layer is obtained by dissolving each raw material in a solvent and mixing them at a predetermined ratio.

The organic solvent used in the present invention depends on the film forming method. For example, as the organic solvent for the gravure coating method, flexographic printing method, and roll coating method, a solvent having a low evaporation rate is suitable. This is because a solvent having a high evaporation rate evaporates before sufficient leveling is performed. The evaporation rate of the solvent is generally evaluated by a relative evaporation rate index with that of butyl acetate being 100. Solvents with this value below 40 are "extremely slow"
It is classified as a solvent having an evaporation rate, and such a solvent is preferable as an organic solvent for a gravure coating method, a flexographic printing method, and a roll coating method. For example, ethyl cellosolve (ethylene glycol monoethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), cellosolve acetate (ethylene glycol monoethyl ether acetate), carbitol (diethylene glycol monoethyl ether), hexylene glycol, diethylene glycol, tripropylene glycol, Examples thereof include diacetone alcohol and tetrahydrofurfuryl alcohol.

The solvent of the coating solution used in the present invention desirably contains at least one such solvent. However, in order to adjust the viscosity and surface tension of the coating solution, a plurality of the above solvents are used. No problem. In addition, solvents having a high evaporation rate and a relative evaporation rate exceeding 100, such as methanol (610) and ethanol (34)
Solvents such as 0), n-propanol (110), isopropanol (300) may be added to the above-mentioned solvents having a relative evaporation rate index of 40 or less.

The coating method used in the present invention is not particularly limited, and examples thereof include a spin coating method, a dip coating method, a spray coating method, and a printing method. In particular, printing methods such as a gravure coating method, a flexographic printing method, a roll coating method, and a screen printing method are preferable because of high productivity and good use efficiency of the coating liquid composition.

The above-mentioned coating solution for an ultraviolet absorbing film is applied on a glass substrate by the above-mentioned coating method, and then, at a temperature of 100 ° C. to 400 ° C. in an oxidizing atmosphere, for 5 to 5 hours.
Heat treatment for 200 minutes, then apply the coating solution for the upper layer colored film by the above-mentioned coating method, and thereafter similarly heat-treat at a temperature of 100 ° C. to 400 ° C. for 5 to 200 minutes in an oxidizing atmosphere. To precipitate gold fine particles for coloring. Further, by baking at a temperature of 500 to 700 ° C. or more for 10 seconds to 5 minutes, an ultraviolet absorbing film and an upper colored film thereon are formed.

The above-mentioned UV absorbing film coating solution is applied,
After drying, further applying a coating liquid for an upper layer, and applying a masking coating as necessary to the dried glass plate, and then performing a bending and / or heat strengthening step, the film firing is performed by the bending and / or heat treatment. It can also be used in the strengthening step, and no special film firing is required.

The types and mixing ratios of these titanium, cerium and silicon raw materials determine the miscibility and stability of the solvent and the gold fine particles for coloring, the refractive index, color and reflection color tone optically, and the mechanical resistance. It is preferable to determine in consideration of abrasion and chemical durability.

In the present invention, an unreinforced glass plate, a tempered glass plate, a laminated glass plate, a double-layer glass plate, etc., having a colored transparent soda lime silicate glass composition as a glass substrate are preferably used. Is a colored glass plate that blocks heat rays, and the transmitted light is-in Lab notation.
A value of a from 9.0 to -2.0, chromaticity of b from -4.0 to 4.0, more preferably a value of a from -7.0 to -3.0;
It has a chromaticity of b of -1.0 to 4.0, is colored light green, and has a transmittance of 10 to 70% for ultraviolet light having a wavelength of 370 nm.
And the sunlight transmittance (also called solar transmittance) is 20 to 8
0%, and a glass sheet for automobile windows having a thickness of 1.5 to 5.5 mm is preferably used.

In the present invention, the transmission color is neutral gray and the visible light transmittance is 70% or more by combining the coloring with the fine gold particles and the ultraviolet shielding with the ultraviolet absorbent.
A UV blocking colored glass having a sunlight transmittance of 55% or less and an ultraviolet transmittance (a value according to ISO 9050; hereinafter simply referred to as Tuv) of 12% or less can be produced. Further, by the two-layer coating, it is possible to realize the control of the reflectance using the interference due to the film configuration and the fine adjustment of the color tone.

[0044]

Next, the present invention will be described in more detail with reference to specific examples.

[Examples 1 to 11] Cerium nitrate hexahydrate was added to ethyl cellosolve (EC) so that the solid content of CeO ₂ became 23.2%, and the mixture was heated to 90 ° C and treated for 1 hour. . This solution was used as a cerium nitrate stock solution.

2 mol of acetylacetone was added dropwise to 1 mol of the stirring titanium isopropoxide with a dropping funnel. This solution was used as a titanium oxide stock solution. This is TiO ₂
16.5% solids.

To 50 g of ethyl silicate ("Ethyl silicate 40" manufactured by Colcoat), 6 g of 0.1N hydrochloric acid and 44 g of ethyl cellosolve were added, and the mixture was stirred at room temperature for 2 hours.
This solution was used as a silicon oxide stock solution. This amounts to 20% SiO ₂ solids. Chloroauric acid tetrahydrate was dissolved in ethyl cellosolve to a concentration of 10% by weight to obtain a chloroauric acid stock solution.

The above-mentioned cerium nitrate stock solution, titanium oxide stock solution, and silicon oxide stock solution were each taken and mixed in the amounts shown in Table 1, and finally, ethyl cellosolve was added in the amounts shown in Table 1,
Three types of coating liquids 1A to 1C each having an oxide solid content of 8.5% by weight were prepared. This is used in Examples 1 to 11 as shown in Table 1.

Further, 0.05 g of cerium nitrate stock solution, 0.05 g of titanium oxide stock solution, and 1.90 g of silicon oxide stock solution were mixed, and 6.70 g of ethyl cellosolve (EC) was added.
g was added to prepare a coating liquid 2A.

Further, 0.13 g of cerium nitrate stock solution, 0.12 g of titanium oxide stock solution and 2.25 g of silicon oxide stock solution were mixed, 6.3 g of ethyl cellosolve was added, and finally 1.2 g of chloroauric acid stock solution was added to prepare coating solution 2B.

The above prepared coating liquids 1A to 1C were applied to a green glass substrate having a thickness of 4.9 mm and a size of 10 cm × 10 cm (glass composition (% by weight); SiO ₂ 71.0, Al ₂ O _3).
1.53, Fe ₂ O ₃ 0.52, CaO 8.62, MgO 4.0
6, Na ₂ O 12.3, K ₂ O 0.76, refractive index 1.51, visible light transmittance Ya = 76.0%, sunlight transmittance Tg = 51.6%, ultraviolet transmittance (Tuv (ISO)) 24.3%, visible light reflectance Rg = 6.9%, transmission color tone; green, Lab color system chromaticity a = -6.5, b
= 0.5, transmitted light dominant wavelength (C light source) 500nm, transmitted light stimulation purity Pe
(C light source) 2.49%, chromaticity of reflected light a = -1.7, b = -0.7) was spin-coated at 1500 rpm for 15 seconds on one surface.

After air-drying the glass substrate coated with the first layer and heat-treating it at 250 ° C. for 2 hours, the coating liquid 2A for Examples 1 to 9 was applied on the first layer.
In each of Examples 10 and 11, the coating liquid 2B was spin-coated at a rotation speed of 1200 to 2000 rpm for 15 seconds, as shown in Table 2, to form a second layer. After air drying, heat treated at 250 ° C for 2 hours,
Gold fine particles in the second layer were precipitated. At 720 ° C
Baking was carried out for 20 seconds to obtain a glass plate coated with an ultraviolet absorbing colored film having a gray color with a transmitted color of gray.

With respect to this glass plate, the film composition, thickness and refractive index of the ultraviolet ray absorbing film (lower layer) as the first layer and the colored film (upper layer) as the second layer are shown in Table 3, and the visible light transmittance was shown. Ya, sunlight transmittance Tg, ultraviolet transmittance Tuv, L
Table 4 shows the chromaticities a and b (transmitted chromaticity) and transmitted light chroma (a ² + b ² ) ^1/2 of the transmitted light in the ab display, which are respectively shown on the glass surface side (the surface coated with the ultraviolet absorbing colored film). When light is projected from the opposite side), the visible light reflectance (glass surface visible light reflectance), the chromaticity a and b (glass surface reflection chromaticity) of the reflected light in Lab display, and the saturation of the reflected light (A ² + b ² ) ^1/2
(Glass surface reflection saturation), and the visible light reflectance (film surface visible light reflectance) and the chromaticity a, b of the reflected light in Lab display when light is projected from the ultraviolet absorbing colored film surface side, respectively. Table 5 shows the (reflection chromaticity of the film surface). The obtained ultraviolet-absorbing colored film showed good results in chemical resistance and abrasion resistance. The film thickness was measured using a stylus meter. The visible light transmittance, sunlight transmittance, and visible light reflectance are JI
According to SR 3106, the UV transmittance is ISO 905
According to 0, the transmission chromaticity and the reflection chromaticity are JIS Z87.
29, respectively.

The obtained glass plate coated with an ultraviolet absorbing colored film has a visible light transmittance of 70% or more, an ultraviolet light transmittance Tuv of 12% or less, a sunlight transmittance Tg of 55% or less, and a glass surface visible of 7% or less. It has a light reflectance of 9% or less on the film surface and a visible light reflectance. Its color tone has a transmitted light saturation of 5.0 or less, and a glass surface reflected light saturation of 5% or less. It can be seen that both the glass surface reflection tones are gray.

[0055]

TABLE 1 ============================== Kotiku Bu example silicon oxide titanium oxide, cerium EC solution number stock (g) Stock solution (g) Stock solution (g) (g) -------------------------- 1.59 1.68 5.74 1B 5-6 0.83 1.76 1.87 5.49 1C 7-9 0.56 1.80 1.90 5.74 ==============================

[0056]

[Table 2] Second layer coating conditions ========= Example Scan condition No. (rpm) 1 1400 2,5,8 1600 3,10 1800 4,6 , 9, 11 2000 7 1200 =========

[0057]

[Table 3] =================================== Example First Layer (Lower Layer) | Two layers (upper layer) No. SiO ₂ TiO ₂ CeO ₂ film thickness Refractive index | SiO ₂ TiO ₂ CeO ₂ Au film thickness Refractive index (wt%) (wt%) (wt%) (nm) | (wt%) (wt %) (wt%) (wt%) (nm) ------------------------------------ 23.2 30.8 45.7 130 1.87 84.3 1.9 2.8 11.0 68 1.48 2 23.2 30.8 45.7 130 1.87 84.3 1.9 2.8 11.0 62 1.48 3 23.2 30.8 45.7 130 1.87 84.3 1.9 2.8 11.0 57 1.48 4 23.2 30.8 45.7 130 1.87 84.3 1.9 2.8 11.0 53 1.48 5 19.5 32.3 48.2 130 1.91 84.3 1.9 2.8 11.0 62 1.48 6 19.5 32.3 48.2 130 1.91 84.3 1.9 2.8 11.0 53 1.48 7 13.1 34.9 52.0 120 1.97 84.3 1.9 2.8 11.0 72 1.48 8 13.1 34.9 52.0 120 1.97 84.3 1.9 2.8 11.0 62 1.48 9 13.1 34.9 52.0 120 1.97 84.3 1.9 2.8 11.0 53 1.48 10 23.2 30.8 45.7 130 1.87 80.8 3.6 5.3 10.3 73 1.50 11 23.2 30.8 45.7 130 1.87 80.8 3.6 5.3 10.3 67 1.50 = ==================================

[0058]

[Table 4] ================================= Implementation Visible Light Sun Ray Ultraviolet Transmitted Light Chromaticity Transmitted Light Example Transmittance Transmittance Transmittance a / b Saturation number Ya (%) Tg (%) Tuv (%) (a ² + b ² ) ^1/2 −−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−− 1 70.9 49.5 10.3 -3.36 / 0.67 3.43 2 71.3 49.7 10.6 -3.06 / -0.05 3.06 3 71.2 49.8 10.7 -2.66 / -0.39 2.69 4 71.3 48.5 11.0 -2.45 / -0.56 2.51 5 71.3 48.7 9.8 -1.79 / 0.19 1.80 6 71.7 48.9 9.9 -1.88 / 0.80 2.04 7 70.4 48.9 10.1 -2.27 / 0.05 2.27 8 71.3 49.3 10.3 -1.58 / -0.54 1.67 9 71.9 49.5 10.5- 1.77 / 0.08 1.77 10 72.2 48.8 10.0 -3.88 / 1.19 4.06 11 72.6 49.3 10.2 -3.53 / 0.46 3.56 ============================ ======

[0059]

[Table 5] ================================= Example Glass Surface Glass Surface Glass Surface Film Surface Film Surface No.Visible light Reflected chromaticity Reflected chroma Visible light Reflected chromaticity Reflectivity a / b (a ² + b ² ) ^1/2 Reflectivity a / b (%) (%) −−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−− 1 6.15 3.55 / -0.58 3.60 6.39 0.56 / 5.27 2 6.44 1.27 / 1.45 1.93 6.97 -2.99 / 7.86 3 6.76 -0.72 / 2.98 3.07 7.59 -5.96 / 9.52 4 6.92 -2.22 / 3.30 3.98 8.06 -7.89 / 9.62 5 6.49 -1.34 / 2.18 2.56 7.16 -8.41 / 7.82 6 6.44 -2.87 / 0.31 2.89 7.53 -10.26 / 5.22 7 6.49 1.12 / 1.95 2.25 6.43 -1.78 / 6.89 8 6.40 -2.16 / 3.20 3.86 6.79 -8.09 / 7.72 9 6.31 -2.94 / 1.79 3.44 7.03 -9.56 / 5.35 10 6.53 4.47 / -1.56 4.73 6.81 2.52 / 3.69 11 6.45 2.74 / 0.63 2.81 7.00 -0.98 / 6.84 =================================

[Comparative Examples 1 to 3] 2.5 g of silicon oxide stock solution
Then, 5.9 g of ethyl cellulov (EC) was added to the mixture, and then trimethylol cellulose acrylate ethylene oxide 6 adduct (EO) was added.
6) was added, and finally 1.5 g of chloroauric acid stock solution was added and mixed and stirred to prepare a coating solution 3.

2.5 g of a silicon oxide stock solution was added, and 5.90 g of ethylcellulob was added thereto. Then, 0.1 g of trimethylol propyl acrylate ethylene oxide 6 adduct was added, and finally 1.3 g of a chloroauric acid stock solution was added, followed by mixing and stirring. Then, a coating liquid 4 was prepared.

2.5 g of the silicon oxide stock solution was added, and 5.90 g of ethylcellulose was added thereto. Then, 0.10 g of trimethylol propyl acrylate ethylene oxide 6 adduct was added, and finally 1.0 g of the chloroauric acid stock solution was added, followed by mixing and stirring. Thus, a coating liquid 5 was prepared.

As shown in Table 6, the coating liquids 3 to 5 prepared above were applied on one surface of the same green glass substrate as used in Example 1 at 100 to 3000 rpm at a speed of 100 to 3000 rpm.
Spin coating was performed for seconds. After drying at 250 ° C 2
Heat treatment was performed for a period of time to precipitate gold fine particles. 720 ° C
For 110 seconds to obtain a glass plate having an ultraviolet absorbing colored film. The obtained glass plates correspond to the coating liquids 3, 4, and 5, respectively, which were used in Comparative Examples 1 and 2, respectively.
2, and 3. For these glass plates, coating liquid composition, coating spin speed, film composition,
Table 6 shows the film thickness and the refractive index, and the visible light transmittance Ya,
Table 7 shows the sunlight transmittance Tg, the ultraviolet transmittance Tuv, the chromaticities a and b (transmitted light chromaticity) of transmitted light in Lab display, and the transmitted light saturation (a ² + b ² ) ^1/2 in Table 7, each of which is a glass surface. When light is projected from the side (the side opposite to the surface covered with the colored film), the visible light reflectance (glass surface visible light reflectance) and the chromaticity a, b (glass surface reflection) by Lab display of the reflected light Chromaticity), the saturation of the reflected light (a ² + b ² ) ^1/2 (glass surface reflection saturation), and the visible light reflectance (film surface visible light) when light is projected from the colored film side, respectively. Table 8 shows chromaticities a and b (film surface reflection chromaticity) of the reflected light in Lab display. The obtained colored film-coated glass plate is 7
The visible light transmittance is 0% or more, and the transmission color tone is also gray, but the ultraviolet transmittance (Tuv) is 21.3 to 21.7%, which is 10% higher than that of the example, and the ultraviolet blocking performance is not sufficient. .

[0064]

[Table 6] ================================ Specific Oxidation EO6 EC Chloride Spine Condition Film Composition (% by Weight) Silicon (g) (g) Auric acid (rpm) SiO ₂ TiO ₂ Au Refractive index Example Stock solution (g) Stock solution (g) (WT%) (WT%) (WT%) −−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−− 12.5 0.1 5.9 1.5 3000 87.5 0.0 12.5 1.46 2 2.5 0.1 5.9 1.3 1000 89.0 0.0 11.0 1.46 3 2.5 0.1 5.9 1.0 1000 91.3 0.0 8.7 1.46 =================================

[0065]

[Table 7] ================================ Comparative Example Visible Light Sun Ray Ultraviolet Transmitted Light Transmitted Light Transmittance Transmittance Transmittance Chroma Saturation Ya (%) Tg (%) Tuv (%) a / b (a ² + b ² ) ^1/2 −−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−− 1 70.8 50.1 21.7 -1.53 / -0.07 1.53 2 70.8 50.4 21.3 -0.67 / 0.52 0.84 3 72.2 50.9 21.8 -1.75 / 0.57 1.84 ====== ===========================

[0066]

[Table 8] ==================================== Ratio Glass Surface Glass Surface Glass Surface Film Surface Light film comparison Visible light reflectivity Reflective chromaticity Reflective chroma Reflectivity Reflective chromaticity Example (%) a / b (a ² + b ² ) ^1/2 (%) a / b −−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 1 7.11 -0.82 / 0.36 1.18 6.53 0.51 / 1.59 2 6.84 -1.38 / -0.11 1.46 5.92 1.18 / -1.05 3 5.69 -1.51 / 0.06 1.55 5.07 0.73 / -1.56 =========================================

[Comparative Examples 4 to 7] Coating solutions shown in Table 9 were prepared, and an ultraviolet absorbing film (except for Comparative Example 4) was formed on the same glass substrate as in the Example under the conditions shown in Table 9. 6 is an upper layer, Comparative Example 7 is a lower layer, and a colored film (Comparative Examples 4 to 6 are a lower layer, Comparative Example 7 is an upper layer) is subjected to spin coating, air drying, heat treatment and baking,
A glass plate having an ultraviolet absorbing colored film was obtained. Tables 10 to 12 show the film composition, refractive index, film thickness and optical characteristics of this glass plate. In Table 11, "T370" represents the transmittance for ultraviolet light having a wavelength of 370 nm. This ultraviolet-absorbing colored film-coated glass plate has a transmission color tone of gray. However, in Comparative Examples 4 to 6, the visible light transmittance is less than 70%, and there is a practical problem. In Comparative Example 7, the visible light transmittance is low. Is 7
Although it is 0% or more, the transmission chromaticity a / b is -7.8 /
1.9, the transmitted light saturation was 8.0, exceeding 5.0, and the transmitted color tone was green, which was far from gray.

[0068]

[Table 9] ================================= Ratio Silicon Oxide Titanium Oxide Cerium Oxide EO6 EC Chloroauric Acid Swine conditions Comparison layer Undiluted solution (g) Undiluted solution (g) Undiluted solution (g) (g) (g) Undiluted solution (g) (rpm) Example −−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−− 4〜6 Lower 2.50 0 0.13 5.6 1.3 1500 7 Lower 0.29 1.56 1.66 0.13 5.6 0 1000 4 Upper 0.29 1.56 1.66 0 6.49 0 1000 5 Upper 0.29 1.56 1.66 0 6.49 0 1500 6 Upper layer 0.29 1.56 1.66 0 6.49 0 2000 7 Upper layer 2.5 0 0 0.13 5.6 1.3 2000 ============================== ====

[0069]

[Table 10] ==================================== Upper Layer | Lower Layer Specific Bending | Comparison Film Composition (Wt%) Fold film thickness | Film composition (wt%) Fold film thickness Example SiO ₂ TiO ₂ CeO ₂ Au ratio (nm) | SiO ₂ TiO ₂ CeO ₂ Au ratio (nm) −−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 4 7.3 36.8 54.9 0 2.02 82 | 89.0 0 0 11.0 1.46 108 5 〃 〃 〃 〃 〃 56 | 〃 〃 〃 〃 〃 108 6 〃 〃 〃 〃 〃 45 | 〃 〃 〃 〃 〃 108 7 89.0 0 0 11.0 1.46 108 | 23.2 30.8 46.0 0 1.89 127 ================== ===================

[0070]

[Table 11] ================================= Ratio Visible Light Sun Ray Ultraviolet 370mn Transmitted Light Transmitted Light Comparison Transmittance Transmittance Transmittance Transmittance Chroma Saturation Example Ya (%) Tg (%) Tuv (%) T370 (%) a / b (a ² + b ² ) ^1/2 −−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−− 4 57.2 42.0 12.9 31.4 0.8 / -3.4 3.5 5 57.3 41.8 13.1 31.5 0.1 / 1.2 1.2 6 58.6 42.6 13.2 31.3 -0.8 / 2.6 2.7 7 75.0 50.0 11.7 28.4 -7.8 / 1.9 8.0 =====================================

[0071]

[Table 12] ================================== Ratio Glass Surface Glass Surface Glass Surface Film Surface Film Surface Comparison Visible light reflectivity Reflective chromaticity Reflective chroma Visible light reflectivity Reflective chromaticity Example (%) (a / b) (a ² + b ² ) ^1/2 (%) a / b −−−− −−− −−−− −−−−−−−−−−−−−−−−−−−−−−−− 4 15.6 -0.6 / 3.9 2.9 24.5 -6.3 / 7.1 5 16.0 -0.9 / -1.3 1.8 24.4 -4.4 / -2.4 6 15.4 -1.1 / -3.4 2.8 22.7 -3.4 / -5.7 7 4.6 0.2 / 0.4 0.9 6.1 2.1 / -3.2 ======================= =============

[0072]

As described above, according to the present invention, a glass article coated with a UV-absorbing colored film having a high visible light transmittance, a neutral gray transmitted light color tone, and an excellent UV cutoff rate can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G02B 5/26 G02B 5/26 5/28 5/28 (72) Inventor Toshifumi Tsujino 3-5-1, Doshomachi, Chuo-ku, Osaka-shi No. Japan Sheet Glass Co., Ltd.

Claims (10)

[Claims] An ultraviolet absorbing film containing, as a main component, silicon oxide 5 to 50, titanium oxide 20 to 70, and cerium oxide 25 to 75 in terms of% by weight, is coated on the surface of the glass substrate. The above-mentioned ultraviolet absorbing film, which contains, in terms of% by weight, silicon oxide 55 to 90, titanium oxide 1.0 to 10, cerium oxide 1.0 to 15, and gold fine particles for coloring 5 to 20 in weight% on the absorbing film. 70% of visible light transmittance formed by forming an upper layer having a lower refractive index than that of
The above-mentioned glass article coated with an ultraviolet absorbing colored film. 2. The glass substrate has a thickness of 1.5 to 5.5 mm and an a of -9.0 to -2.0 expressed in Lab color system.
And chromaticity of transmitted light having a value of b of -4.0 to 4.0, 10
The UV-absorbing colored film-coated glass article according to claim 1, having a UV transmittance (at a wavelength of 370 nm) of ~ 70% and a solar transmittance of 20-80%. 3. The glass substrate has a value of a of -7.0 to -3.0 and a value of -1.0 to 4.0 in a Lab color system.
The ultraviolet-absorbing colored film-coated glass article according to claim 1 or 2, having a transmitted light chromaticity of a value of b. 4. The colored film-coated glass article is calculated from the values of a and b in the Lab color system (a ² +
b ²⁾ UV absorbing colored film-coated glass article according to claim 1 ^{in which 1/2} of the value having a transmission glow of 5.0 or less. 5. The colored film-coated glass article is calculated from the values of a and b in the Lab color system (a ² + b ² ) ^1/2.
The UV-absorbing colored film-coated glass article according to any one of claims 1 to 4, which has a reflected light saturation on the glass surface side, wherein the value of is 10 or less. 6. The colored film-coated glass article is calculated from the values of a and b in the Lab color system (a ² + b ² ) ^1/2.
The glass article coated with an ultraviolet-absorbing colored film according to claim 5, which has a reflected light chroma on the glass surface side, the value of which is 5.0 or less. 7. The glass article coated with an ultraviolet absorbing colored film according to claim 1, wherein the glass article coated with a colored film has an ultraviolet transmittance (Tuv) of 15% or less. 8. The glass article coated with an ultraviolet absorbing colored film according to claim 7, wherein the glass article coated with a colored film has an ultraviolet transmittance (Tuv) of 12% or less. 9. The UV-absorbing colored film-coated glass article according to any one of claims 1 to 8, wherein the colored film-coated glass article has a sunlight transmittance of 55% or less. 10. The ultraviolet absorbing film has a thickness of 1.63 to 2.2.
The upper layer has a refractive index of 1.40 to 1.60 and a thickness of 30 to 120 nm.
The film according to any one of claims 1 to 9, wherein the upper layer has a thickness of 0.90 to 1.17 times the value of the square root of the refractive index of the ultraviolet absorbing film. A glass article coated with an ultraviolet absorbing colored film.